Algae-blended thermoplastic compositions

ABSTRACT

An algae-based thermoplastic composition is provided that includes a protein-rich algae biomass selected from either microalgae, macroalgae or combinations thereof. The protein content is greater than or equal to 15% by weight of the algae biomass and the algae biomass is dried to a moisture content of less than or equal to 15% by weight and having a particle d99 of up to 200 microns. The dried algae biomass is at least 5% by weight of the thermoplastic composition. The composition includes a biodegradable resin configured to exhibit rheological properties suitable for blending with algae including a melting temperature less than 250° C. and a melt flow rate in excess of 0.01 g/10 min.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. patent applicationSer. No. 15/558,303 filed on Sep. 14, 2017, which claims priority toPCT/US2016/22648 filed Mar. 16, 2016 which claims priority to U.S.Provisional application 62/140,880 filed Mar. 31, 2015 the disclosuresof which are incorporated herein by reference in their entirety for allpurposes; this application further claims priority benefit to U.S.Provisional Application No. 62/851,871 filed May 23, 2019, titled ALGAETHERMOPLASTIC COMPOSITION AND PROCESS OF MAKING, the disclosure of whichis incorporated herein by reference in its entirety for all purposes.

BACKGROUND

The present disclosure relates to polymeric compositions that containcertain biodegradable and renewable components. In particular, thepresent disclosure describes, in part, a thermoplastic composition thatincludes algae as relatively low cost feedstock.

Polymer-based films, fibers, or filament structures have been adaptedfor widespread use in many different applications, such as nonwovensheets that can be made into a variety of wipers, disposable absorbentproducts, or protective- and healthcare-related fabrics. For example, inthe infant and child care areas, diapers and training pants havegenerally replaced reusable cloth absorbent articles. Other typicaldisposable absorbent products include feminine care products such assanitary napkins or tampons, adult incontinence products, and healthcare products such as surgical drapes or wound dressings. A typicaldisposable absorbent product generally includes a composite structurehaving a topsheet, a backsheet, and an absorbent structure between thetopsheet and backsheet. These products usually include some type offastening system for fitting the product onto the wearer.

Disposable absorbent products are typically subjected to one or moreliquid insults, such as of water, urine, menses, or blood, during use.As such, the outer cover backsheet materials of the disposable absorbentproducts are typically made of liquid-insoluble and liquid impermeablematerials, such as polyethylene films, that exhibit a sufficientstrength and handling capability so that the disposable absorbentproduct retains its integrity during use by a wearer and does not allowleakage of the liquid insulting the product.

Although current disposable baby diapers and other disposable absorbentproducts have been generally accepted by the public, these productsstill have a need of improvement in specific areas, including disposaland a reduction in petroleum requirements.

Over the years, different kinds of algae have been adapted for a varietyof industrial applications, including neutraceuticals, lipid production,wastewater and air remediation, biomass production, biofuels, biomeal,plastics, foamed packing materials, and pulp and paper.

The algae biotechnology industry is currently focused on using algae toreplace U.S. demand for oil. As a result, available venture funds aremostly directed to research and development of algae production, omegafatty acid, and biofuel extraction processes. However, it is not ontarget yet to utilize algae or biomeal from the biofuel refiningprocesses for plastic manufacturing. Further, thermoplasticprocessability of algae materials is not easily envisioned because itcontains multiple constituents such as proteins, carbohydrates, andlipids, which complicates issues because these substances aretraditionally are handled separately.

SUMMARY

The present disclosure provides for an algae-based thermoplasticcomposition including: (a) a protein-rich algae biomass selected fromeither microalgae, macroalgae or combinations thereof, wherein theprotein content is greater than or equal to 15% by weight of the algaebiomass and the algae biomass is dried to a moisture content of lessthan or equal to 15% by weight and having a particle d99 of up to 200microns, wherein the dried algae biomass is at least 5% by weight of thethermoplastic composition; and (b) a resin can be selected from thegroup consisting of biodegradable polymers, polyesters, polyolefins,thermoplastic elastomers, styrenics, polyamides, polyethers, polyvinylchlorides (PVC), thermoplastic polyurethanes (TPU), polybutyleneadipate-co-terephthalate (PBAT), polyethylene (PE), ethylene-vinylacetate (EVA), their copolymers, and combinations thereof. The resin canbe configured to exhibit rheological properties suitable for blendingwith algae including a melting temperature less than 250° C. and a meltflow rate in excess of 0.01 g/10 min.

In an example, the algae biomass is provided having a protein content ofgreater than 20% by weight. The algae biomass can be include a memberfrom the group consisting of cyanobacteria and a Cyanophyta, Charophyta,Chlorophyta, Phaeophyta, Chrysophyta, Bacillariophyta, Haptophyta, andRhodophyta phylum microalgae. The algae biomass can be sourced from aplurality of algae sources including a member from the group of mineralrich algae consisting of diatoms, coccalithophores, coralline andcombinations thereof.

In another example, the algae biomass includes a dry weight of 15 to 90%protein, 5 to 50% carbohydrates, and 5 to 80% mineral and/or inorganicash content. In another example, the algae biomass comprises a dryweight of 20 to 85% protein, 10% to 45% carbohydrate, and 10 to 75%mineral and/or inorganic ash content. In yet a further example, thealgae biomass includes a dry weight of 25 to 80% protein, 15% to 40%carbohydrate, and 15 to 70% mineral and/or inorganic ash content. Ineven still another example, the algae biomass includes a dry weight of35-50% protein, 5-30% carbohydrate and 25-40% mineral and/or inorganicash content. The algae biomass can be provided as a powder milled to anaverage particle size between 1 and 80 micron.

In an example, the composition includes a compatibilizer provided toincrease compatibility of the algae biomass with the resin, thecompatibilizer having functionalization selected from the groupconsisting of side chain modified polymers, block copolymers, graftedcompatibilizer, reactive compatibilizers with glycidyl methacrylate,butyl acrylate, maleic anhydride groups or coupling agents selected fromthe group consisting of peroxides, isocyanates, and glyoxal. The resincan include a member selected from the group consisting of synthetic,plant-based, bio-based, renewably-sourced, petroleum sourced resins andcombinations thereof.

In a further example, the resin is selected from the group consisting ofpolyesters, polyethylene terephthalate (PET), polybutylene terephthalate(PBT), polyethylene terephthalate glycol (PETG), polytrimethyleneterephthalate (PTT), polycarbonate, biodegradable resins, polylacticacid (PLA), polybutylene succinate (PBS), polybutyleneadipate-co-terephthalate (PBAT), polyhydroxyalkanoates (PHA),polyolefins such as polyethylene (PE), polypropylene (PP), polybutene(PB), polyisobutylene (PIB), thermoplastic elastomers such asthermoplastic polyurethanes (TPU), ethylene vinyl acetate (EVA),thermoplastic polyolefin elastomers (TPO), thermoplastic vulcanizates(TPV), thermoplastic copolyesters (TPE-E), thermoplastic polyamides(TPA), thermoplastic styrenic block copolymers (TPS), thermoplasticester-ether copolymers (TPC), thermoplastic amide-ether copolymers(TPE-A), polyacrylonitrile butadiene styrene (ABS), polyacrylonitrilestyrene acrylate (ASA), polystyrene acrylonitrile (SAN), polystyrenebutadiene (SB), polystyrene (PS) nylon, polyvinyl alcohol (PVA),polyvinylidene chloride (PVDC) and combinations thereof.

The thermoplastic composition can be configured for use in processesselected from injection molding, blow molding, roto molding, cast filmextrusion, blown film extrusion, bun foaming, injection foaming,compression foaming, profile extrusion, steam chest expansion foaming,autoclave foaming and combinations thereof.

The composition can further include a foaming ingredient selected fromthe group of additives consisting of crosslinkers, peroxide-basedcrosslinking agents, isocyanate-based crosslinking agents, sulfur-basedcrosslinking agents, aziridine-based crosslinking agents,dialdehyde-based crosslinking agents, compatibilizers, plasticizers,accelerants, catalysts, blowing agents, and combinations thereof,wherein the foaming ingredient is configured to forming a thermoplasticbiodegradable foam product.

The biodegradable resin can be selected from the group resins consistingof polybutylene adipate-co-terephthalate (PBAT), polybutylene succinate(PBS), polylactic acid (PLA), polyhydroxyalkanoates (PHA), thermoplasticstarch (TPS), and polycaprolactone (PCL).

The present disclosure provides for a solid product including thethermoplastic composition of claim 1, wherein the composition isprovided having a density from 400 to 2500 kg/m3. The foam compositioncan be configured to form a film or fiber defining a thickness from 1micron to 3 cm. The algae biomass composition can be added alongside achemoattractant or swelling agents configured to make non-degradableresins biodegradable such that a biodegradable substrate with anaerobicbiodegradation is produced.

In one example, the present disclosure provides for improvedthermoplastic algae processing by eliminating the presence of theplasticizer and plant polymer, in contrast to previous efforts. Thisdisclosure expands thermoplastic algae technology and securessustainability using renewable and sustainable materials for a bio-basedeconomy.

The present disclosure enables fabricators to use algae as a sustainableand renewable material for plastic manufacturing, to develop a novel andefficient thermoplastic processing method to produce articles using thethermoplastic algae for plastic applications such as, but not limitedto, personal care products, agriculture films, containers, buildingmaterials, electrical apparatus, and automobile parts.

The present disclosure concerns, in part, a thermoplastic compositionthat is desirably substantially biodegradable and yet which is easilyprepared and able to be readily processed into desired final structures,such as films, fibers, or nonwoven structures, or larger extruded ormolded, three-dimensional forms. The disclosure demonstrates anindustrial feasibility for manufacturers to incorporate a significantpercentage of renewable algal biomass into polymer blends for theproduction of biodegradable plastic materials.

According to one aspect, the present disclosure is directed to athermoplastic composition including at least one kind of algae thatconstitutes from about 10 wt. % to about 55 wt. % of the composition,and a polymer that constitutes from about 45 wt. % to about 90 wt. % ofthe composition, wherein the composition is free of plasticizer and freeof plant polymer.

In another aspect, the present disclosure concerns an injection moldedarticle formed from a material including at least one kind of algae thatconstitutes from about 10 wt. % to about 55 wt. % of the composition,and a polymer that constitutes from about 45 wt. % to about 90 wt. % ofthe composition, wherein the material is free of plasticizer and free ofplant polymer.

In yet another aspect, the disclosure pertains to a thermoplasticcomposition including blue-green algae that constitutes from about 10wt. % to about 55 wt. % of the composition, and a polymer thatconstitutes from about 45 wt. % to about 90 wt. % of the composition,wherein the composition is free of plasticizer and free of plantpolymer.

Additional features and advantages of the present disclosure will berevealed in the following detailed description. Both the foregoingsummary and the following detailed description and examples are merelyrepresentative of the disclosure, and are intended to provide anoverview for understanding the disclosure as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURES which accompany the written portion of this specificationillustrate embodiments and method(s) of use for the present disclosureconstructed and operative according to the teachings of the presentdisclosure.

FIG. 1 is flow chart of a method of forming a thermoplastic-algaecomposition according to the present disclosure.

The various embodiments of the present disclosure will hereinafter bedescribed in conjunction with the appended drawings, wherein likedesignations denote like elements.

DETAILED DESCRIPTION

The term “biodegradable,” as used herein refers generally to a materialthat can degrade from the action of naturally occurring microorganisms,such as bacteria, fungi, and algae; environmental heat; moisture; orother environmental factors. If desired, the extent of biodegradabilitycan be determined according to ASTM Test Method 5338.92.

The term “renewable” as used herein refers to a material that can beproduced or is derivable from a natural source that is periodically(e.g., annually or perennially) replenished through the actions ofplants of terrestrial, aquatic, or oceanic ecosystems (e.g.,agricultural crops, edible and non-edible grasses, forest products,seaweed, or algae), or microorganisms (e.g., bacteria, fungi, or yeast).

In the two-kingdom system, algae, like bacteria and fungi, were oftenassigned to the plant kingdom. Properties qualifying the algae for theplant kingdom was its ability to make its own food by photosynthesis,its structural similarity to land plants, and the fact that the largerforms were observed to be sedentary. Eukaryotic unicellular organismswith chloroplasts were also called plants. The major groups ofeukaryotic algae are the green algae, diatoms, red algae, brown algae,and dinoflagellates. They are classified as protista. Another group, theblue-green algae, is the cyanobacteria.

Green algae are the algae most closely related to plants. They have thesame pigments (chlorophyll a and b and carotenoids), the same chemicalsin their cell walls (cellulose), and the same storage product (starch)as plants. Green algae can be unicellular or form filaments, nets,sheets, spheres, or complex moss-like structures. There are bothfreshwater and marine species. Some species of green algae live on snow,or in symbiotic associations as lichens, or with sponges or otheraquatic animals. Edible green algae include Chlorella and sea lettuce.There are at least seventeen thousand species of green algae.

The photosynthesis carried out by algae is very important to thebiosphere because it reduces the amount of carbon dioxide and increasesthe amount of oxygen in the atmosphere. In recent years, there has beena movement to cultivate algae to store carbon dioxide released frompower plants and to use nutrients from effluents discharged fromwastewater treatment facilities to control air and water pollutions. Indoing so, algae biomass is created and can be harvested for multipleapplications.

Algae are the base of the aquatic food chain. For example, as fish eatalgae, the omega-fatty acids in algae are accumulated in the fish andare extracted as human nutrient supplements. Marine algae such as noriand kelp have been consumed by humans for thousands of years. Largebrown seaweeds such as Saccharina japonica and Undaraia pinntifida arenow cultivated in China, Japan, and Korea for food applications. Some ofthe seaweeds have antioxidant, anticoagulant, and anti-diabetesactivities, even showing a UV (ultraviolet) light protection capacity.The most recent advancement in algae utilization is to refine it forbiofuel due to limited fossil fuel resources and the high cost ofpetroleum (Bullis, 2008). Biomeal, a leftover waste material fromalgae-to-biofuel processing, is normally used for animal feeds. In somecases, biomeal is treated as a waste and disposed of in sanitarylandfills. Methods exist to manufacture pet or animal foods using suchthis waste product that includes the cell carcasses that remain afterone or more essential fatty acids such as docosahexaenoic acid (DHA)have been extracted from lysed algae cells such as Crypthecodiniumcohnii.

Algae biomass is expected to be abundant in the future because it isincreasingly used to abate air pollution and climate change byassimilating carbon dioxide and by taking up excessive nutrients in theeffluent discharged from wastewater treatment facilities. When cheap oilbecomes scarce, algae will be one of the sustainable and renewableresources used for biofuel refining. As a result, algae biomass and itsbiomeal (leftover waste material from algae biofuel refining) areincreasingly available to be processed for other uses, including plasticmanufacturing. This opportunity enables a strategy to use an alternativeresource, which is important to any businesses that currently rely onpetroleum for plastics manufacturing.

In the present disclosure, thermoplastic blends of synthetic polymerssuch as LLDPE, EVA, and PLA are each compounded with algae biomasswithout relying on the use of plasticizers such as glycerin or plantpolymers such as starch or soy protein. This technology enablescompounding those materials for bioplastics manufacturing at a reducedcost, without the need of plasticizers. The resultant blends aresuperior in mechanical properties for injection molded articles becausethe presence of plasticizers facilitates compounding processes butweakens the mechanical properties of the final blended composites.

Typical approaches to using algae include modifying/pulverizingsynthetic polymers and grinding/extracting fibrous algae materials formaking foams and composites. None of these approaches is viable forscale up or industrial applications except for those used to employ redalgae for pulp and paper manufacturing. Previous efforts to incorporatealgae in polymers required the addition of plant polymers such asstarch, wheat gluten, and soy protein, which are chemically compatibleand physically miscible with the selected algae, to facilitatethermoplastic conversion processes when a plasticizer such as glycerinis used. This disclosure improves thermoplastic algae processing byeliminating the presence of the plasticizer and plant polymers. Inaddition, this disclosure enables thermoplastic processing of algaematerials, and developing material components such as films, fibers, andinjection molded articles for personal care product and otherapplications. The whole processing equipment and operational conditionsdemonstrated in this disclosure are scalable to a large productionwhenever it is in demand.

Articles such as thermoplastic films useful for personal care productapplications are successfully made from a blend of polymers and algaeusing an extrusion technology. The thermoplastic composition is capableof being extruded into films, filaments, or fibers that can beincorporated in various nonwoven structures. Such nonwoven structurescan be adapted for use in a disposable absorbent product, such asincluding cleaning wipes, diapers, or other personal hygiene or personalcare products that can absorb body fluids, for instance, training pants,adult incontinence products, or feminine hygiene pads. Additionally, thethermoplastic compositions can be used to form molded goods, such assolid forms, tubing, panels, or containers.

An advantage of the processing and plastic fabrication method accordingto the disclosure complements industrially preferred techniques and canbe more easily scaled up for commercial production. Potentialapplications of the present compositions can include moldedthermoplastic materials made for plastic containers (e.g., for wet wipetubs), elastomeric materials (e.g., for disposable diapers), or films(e.g., for feminine pads and diapers), or flexible packaging materials(e.g., for plastic bags). Methods of making these components can be bymeans of injection molding or thermal plastic extrusion.

Demonstrative examples for thermoplastic polyester films include acomposition of algae that displays desirable mechanical properties. Theplasticized algae materials show distinctive melting temperatures andmultiple glass transition temperatures, which are not observable formost plant polymers such as starch, wheat gluten and soy protein afterthey have been converted into thermoplastic materials.

In some aspects, according to the present disclosure, the thermoplasticpolymer composition can include a plasticized algae biomass and athermoplastic polymer. The thermoplastic polymers can include a varietyof broad classes of polymers, for example, renewable polymers (e.g.,poly-lactic acid (PLA); poly-hydroxyalkanoate (PHA), such aspoly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate),poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV),poly(3-hydroxybutyrate-co-3-hydroxyhexanoate),poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), etc.), biodegradablepolymers (e.g., aliphatic-aromatic co-polyester, poly(butylenesuccinate) (PBS), polycaprolactone (PCL), etc.), or non-biodegradablepolymers (e.g., polyolefins (e.g., polypropylene, polyethylene),polystyrene, polyesters, polyvinyl-chloride (PVC),poly(acrylonitrile-co-butadiene-co-styrene) (ABS), thermoplasticelastomers, such as polyurethane, styrenic block copolymers (SBC, fromKRATON Polymers LLC, Houston, Tex.), etc.

Illustrative of petroleum-based synthetic polymers, for instance,saturated ethylene polymers can be homopolymers or copolymers ofethylene and polypropylene and are essentially linear in structure. Asused herein, the term “saturated” refers to polymers that are fullysaturated, but also includes polymers containing up to about 5%unsaturation. The homopolymers of ethylene include those prepared undereither low pressure, i.e., linear low density or high densitypolyethylene, or high pressure, i.e., branched or low densitypolyethylene.

The high density polyethylenes are generally characterized by a densitythat is about equal to or greater than 0.94 grams per cubic centimeter(g/cc). Generally, the high density polyethylenes useful in the presentdisclosure have a density ranging from about 0.94 g/cc to about 0.97g/cc. The polyethylenes can have a melt index, as measured at 2.16 kgand 190° C., ranging from about 0.005 decigrams per minute (dg/min) to100 dg/min. Desirably, the polyethylene has a melt index of 0.01 dg/minto about 50 dg/min and more desirably of 0.05 dg/min to about 25 dg/min.Alternatively, mixtures of polyethylene can be used as the base resin inproducing the graft copolymer compositions, and such mixtures can have amelt index greater than 0.005 dg/min to less than about 100 dg/min.

The low density polyethylene has a density of less than 0.94 g/cc and isusually in the range of 0.91 g/cc to about 0.93 g/cc. The low densitypolyethylene polymer has a melt index ranging from about 0.05 dg/min toabout 100 dg/min and desirably from 0.05 dg/min to about 20 dg/min.Ultra low density polyethylene can be used in accordance with thepresent disclosure. Typically, ultra-low density polyethylene has adensity of less than 0.90 g/cc.

Generally, polypropylene has a semi-crystalline structure having amolecular weight of about 40,000 or more, a density of about 0.90 g/cc,a melting point of 168° to 171° C. for isotactic polypropylene and atensile strength of 5000 psi. Polypropylene can also have othertacticities including syndiotactic and atactic.

The above polyolefins can also be manufactured by using the well-knownmultiple-site Ziegler-Natta catalysts or the more recent single-sitemetallocene catalysts. The metallocene catalyzed polyolefins have bettercontrolled polymer microstructures than polyolefins manufactured usingZiegler-Natta catalysts, including narrower molecular weightdistribution, well controlled chemical composition distribution,co-monomer sequence length distribution, and stereoregularity.Metallocene catalysts are known to polymerize propylene into atactic,isotactic, syndiotactic, isotactic-atactic steroblock copolymer.

Copolymers of ethylene that can be useful in the present disclosure caninclude copolymers of ethylene with one or more additionalpolymerizable, unsaturated monomers. Examples of such copolymersinclude, but are not limited to, copolymers of ethylene and alphaolefins (such as propylene, butene, hexene or octene) including linearlow density polyethylene, copolymers of ethylene and vinyl esters oflinear or branched carboxylic acids having 1-24 carbon atoms such asethylene-vinyl acetate copolymers, and copolymers of ethylene andacrylic or methacrylic esters of linear, branched or cyclic alkanolshaving 1-28 carbon atoms. Examples of these latter copolymers includeethylene-alkyl (meth)acrylate copolymers, such as ethylene-methylacrylate copolymers.

Similar to the foregoing examples of ethylene polyolefin species, inother iterations, the algae or plasticized algae can be combined with apolymer selected from, for instance, polyether, polyvinylchloride (PVC),polystyrene, polyurethane, ethylene vinyl acetate copolymers, and nylonmaterials. The material can be present in similar proportions as thenon-biodegradable components of the composition as stated above.

The algae can be bleached with reduced color ranging from light yellowto off-white. Bleaching of algae can be conducted by a number of methodssuch as chlorine-based bleaching methods used in typical pulp bleachingprocess or enzyme-based bleaching method.

Examples Materials

Linear low density polyethylene (LLDPE), LL1500, was purchased fromPlastic Solutions, Inc., Roswell, Ga. Its melt flow index is 150 g/10min obtained under 190° C./2.16 kg conditions (D-1238). Ethylene vinylacetate (EVA) copolymer, EVATANE 28-150 copolymer, was purchased fromArkema in France. Its vinyl acetate content is 27-29% wt and its meltflow index is 135-175 g/10 min obtained under 190° C./2.16 kgconditions. Polylactic acid, NATUREWORKS 3251D biopolymer, was purchasedfrom NatureWorks, Minnetonka, Minn. Its melt flow index is 70-85 g/10min obtained under 190° C./2.16 kg conditions. LOTADER 5500 terpolymer,which was purchased from Arkema (www.arkema.com), is an acrylicester-maleic anhydride terpolymer. It has an ethyl acrylate content of20% with a melt index of 20 g/10 min under 190° C./2.16 kg conditions.Organic, food-grade blue-green algae that has been spray dried waspurchased from www.nuts.com with a SKU of OS-F-SD-1.

Equipment

The disclosed samples were made using a THEYSOHN TSK 21 mm twin screwextruder at the Polymer Center of Excellence, Charlotte, N.C. Thisextruder is equipped with segmented screws that can be quicklyreconfigured to meet specific needs and clamshell design makes screwchanges and cleanouts quick and easy. It is set up with a K-Tron twingravimetric feeder to feed polymers and a side feeder to feed algaebiomass.

A twin screw extruder (40 mm) from ENTEK (Lebanon, Oreg.) was also usedto make samples in Examples 6 and 7.

Injection Molded Article: Injection molding is one of the most importantprocesses used to manufacture plastic products. The injection moldingprocess is ideally suited to manufacture mass-produced parts of complexshapes requiring precise dimensions. The major components for anyinjection molding machines are the plasticating unit, clamping unit, andthe mold. A Boy 22D injection machine with dipronic solid state controlfrom Boy Machines, Inc. (Exton, Pa.) was used to make mold samples inthis invention disclosure. The clamping force was 24.2 metric tons, theplasticating unit was 24 mm, and a shot size was 1.2 oz (PS). The moldused was an ASTM D638 standard test specimen mold from Master PrecisionProducts, Inc. (Greenville, Mich.). This mold contains a tensile type Ispecimen, a round disk, a tensile type V specimen, and izod bar, whichcan be formed at once during single injection operation.

Example 1

The temperature profile setup for the THEYSOHN TSK 21 mm twin screwextruder (Twin Screw Extruders, Inc., Charlotte, N.C.) was 320° F. fromZones 1 to 5 and die. The feeding rate for a blend of LLDPE and EVA(30/20) through the main K-Tron feeder was at 5 lbs./hr. and algaefeeding rate was 5 lbs./hr. through the side feeder. Therefore, theratio of polymer to algae is 50/50 in the final blend. The actualtemperature profile was 319, 317, 318, 323, 311, and 290° F. from Zone 1to die. Vacuum was run at the last port to release moisture. The strandfrom the die was granulated for injection molding.

Examples 2

The processing used in Example 2 was the same as that used in Example 1.A blend of LLDPE and EVA was 35/15, combined as one component for 50%,and the algae was kept the same as in Example 1 at 50%. The actualtemperature profile was 320, 320, 320, 320, 300, and 290° F. from Zone 1to die.

Example 3

The processing used in Example 3 was the same as that used in Example 1.A blend of LLDPE and EVA was 40/10, combined as one component for 50%,and the algae was kept the same as in Example 1 at 50%. The actualtemperature profile was 316, 318, 319, 321, 300, and 290° F. from Zone 1to die.

Example 4

The processing used in Example 4 was the same as that used in Example 1.LLDPE was used at 50%, and the algae was kept the same as in Example 1at 50%. The actual temperature profile was 318, 318, 316, 317, 300, and290° F. from Zone 1 to die.

Example 5

The processing used in Example 5 was the same as that used in Example 1.PLA was used at 50%, and the algae was kept the same as in Example 1 at50%. The actual temperature profile was 320, 350, 350, 350, 350, and250° F. from Zone 1 to die.

Example 6

The thermoplastic blend composition in this Example 6 contained 55%algal biomass, 38% EVA, and 7% additive. The additive was made of 2.5%01 (odor inhibitor), 2.5% MS (moisture scavenger), and 2% LOTADER 5500terpolymer. LOTADER 5500 terpolymer is a reactive ethylene-acrylateterpolymer that is used as a compatibilizer or coupling agent. An ENTEKextruder (40 mm) from ENTEK (Lebanon, Oreg.) was used to make thesample, the extruder comprising 13 zones. The temperature profile fromzones 1 to 13 was 88, 399, 399, 350, 338, 320, 309, 298, 298, 299, 298,297, and 299° F. The extruder speed was 140 rpm and the torque was 31 to32%.

Example 7

The thermoplastic blend composition in this Example 7 contained 45%algal biomass, 48% EVA, and 7% additive. The additive was made of 2.5%01 (odor inhibitor), 2.5% MS (moisture scavenger), and 2% LOTADER 5500terpolymer. LOTADER 5500 terpolymer is a reactive ethylene-acrylateterpolymer that is used as a compatibilizer or coupling agent. An ENTEKextruder (40 mm) from ENTEK (Lebanon, Oreg.) was used to make thesample, the extruder comprising 13 zones. The temperature profile fromzones 1 to 13 was 88, 399, 399, 350, 338, 320, 309, 298, 298, 299, 298,297, and 299° F. The extruder speed was 120 rpm and the torque was 37%.

Results

The pelletized samples from Examples 1 to 7 were injection molded in themanner described above. The processing temperature profile for heatingbands 1 to 3 was 145, 148, and 150° C., respectively. The nozzletemperature was 153° C., and the mold temperature was set at 80° F. Theinjection molding cycle began when the mold was closed. At this point,the screw moved forward and injected the resins through the nozzle andinto sprue. The material filled the mold (runners, gates, and cavities).During the packing phase, additional material was packed into thecavities while a holding pressure at 95% for 15 seconds was maintainedto compensate for material shrinkage. The material was cooled andsolidified in the mold while the screw rotated counterclockwisebackward, melting the plastic for the next shot. The mold opened and theparts were ejected with a cycle time of 40 seconds. The next cycle beganwhen the mold closed again. All four components (tensile type Ispecimen, round disk, tensile type V specimen, and izod bar) weresuccessfully made.

In a first particular aspect, thermoplastic composition includes atleast one kind of algae that constitutes from about 10 wt. % to about 55wt. % of the composition, and a polymer that constitutes from about 45wt. % to about 90 wt. % of the composition, wherein the composition isfree of plasticizer and free of plant polymer.

A second particular aspect includes the first particular aspect, whereinthe algae is blue-green algae.

A third particular aspect includes the first and/or second aspect,wherein the polymer is linear low density polyethylene.

A fourth particular aspect includes one or more of aspects 1-3, whereinthe polymer is ethylene vinyl acetate copolymer.

A fifth particular aspect includes one or more of aspects 1-4, whereinthe polymer is polylactic acid.

A sixth particular aspect includes one or more of aspects 1-5, furtherincluding an additive, wherein the additive includes one or more of anodor inhibitor, a moisture scavenger, and a compatibilizer.

A seventh particular aspect includes one or more of aspects 1-6, whereinthe algae is a bleached algae with reduced color ranging from lightyellow to off-white.

In an eighth particular aspect, an injection molded article is formedfrom a material including at least one kind of algae that constitutesfrom about 10 wt. % to about 55 wt. % of the composition, and a polymerthat constitutes from about 45 wt. % to about 90 wt. % of thecomposition, wherein the material is free of plasticizer and free ofplant polymer.

A ninth particular aspect includes the eighth particular aspect, whereinthe algae is blue-green algae.

A tenth particular aspect includes the eighth and/or ninth aspect,wherein the polymer is linear low density polyethylene.

An eleventh particular aspect includes one or more of aspects 8-10,wherein the polymer is ethylene vinyl acetate copolymer.

A twelfth particular aspect includes one or more of aspects 8-11,wherein the polymer is polylactic acid.

A thirteenth particular aspect includes one or more of aspects 8-12,further including an additive, wherein the additive includes one or moreof an odor inhibitor, a moisture scavenger, and a compatibilizer.

A fourteenth particular aspect includes one or more of aspects 8-13,wherein the algae is a bleached algae with reduced color ranging fromlight yellow to off-white.

In a fifteenth particular aspect, a thermoplastic composition includesblue-green algae that constitutes from about 10 wt. % to about 55 wt. %of the composition, and a polymer that constitutes from about 45 wt. %to about 90 wt. % of the composition, wherein the composition is free ofplasticizer and free of plant polymer.

A sixteenth particular aspect includes the fifteenth aspect, wherein thepolymer is linear low density polyethylene.

A seventeenth particular aspect includes the fifteenth and/or sixteenthaspects, wherein the polymer is ethylene vinyl acetate copolymer.

An eighteenth particular aspect includes one or more of aspects 15-17,wherein the polymer is polylactic acid.

A nineteenth particular aspect includes one or more of aspects 15-18,further including an additive, wherein the additive includes one or moreof an odor inhibitor, a moisture scavenger, and a compatibilizer.

The present disclosure provides for algae-based thermoplasticcompositions and methods of making such algae-based thermoplasticcompositions. Moreover, these algae-based thermoplastic compositionshave usefulness in foam-type applications. The algae-based thermoplasticcompositions have been developed to produce commercially viable productsincluding foams, fibers, films, injection molded articles, blownarticles, cast parts, and other plastic articles consistent with a setof specifications set by industry. In some examples, the thermoplasticcompositions improve foam product and end-product characteristics suchas tear strength, adhesive bonding strength, biodegradability,elongation, and other properties. Foam products means a product composedat least partially of a polymer formed by trapping pockets of gas inliquid or solid. A foam end-product means a product or portion of aproduct that incorporates the produced foam. Examples of foam caninclude, but not limited to: thermoplastic elastomer, thermoplasticpolyurethane (TPU), polybutylene adipate-co-terephthalate, polyethylene,and/or ethylene-vinyl acetate (EVA) foam. Examples of foam end-productsinclude a cushion or a shoe component such as an insole, midsole oroutsole.

Co-owned and pending patent applications: Ser. No. 15/261,767 filed Sep.9, 2016 titled “ALGAE-DERIVED FLEXIBLE FOAM, AND A METHOD OFMANUFACTURING THE SAME”; Ser. No. 15/356,213 filed Nov. 18, 2016 titled“ALGAE-DERIVED FLEXIBLE FOAM, AND A METHOD OF MANUFACTURING THE SAME”;and Ser. No. 16/396,370 filed Apr. 26, 2019 titled “ELASTOMER COMPOSITEINCLUDING ALGAE BIOMASS FILLER” describe various embodiments ofalgae-based polymer compositions and materials and are herebyincorporated by reference in their entirety.

Referring to the process of FIG. 1, a flowchart illustrating a processfor forming an exemplary algae-based thermoplastic is shown. Process 100starts with step 110 which includes grinding an algae biomass. This caninclude forming an algae powder having an average diameter particle sizeof up to 200 microns. From there the process moves to step 120 where thealgae biomass is dried forming a dried or relatively dried algae biomasspowder. The dried algae biomass should have a moisture content of 15% orless. The process continues to step 130 where the thermoplastic resin ispremixed and preheated to a desired temperature and viscosity forming amolten thermoplastic. In an example, the resin is premixed and preheatedto a temperature in a range of (90° C.-250° C.) for (1 to 30 minutes) toachieve a polymer viscosity sufficient to accept a particulate fillerwhere in the melt flow rate of the polymer is in excess of 0.01 g/10min. The process continues to step 140 where the algae biomass from step120 is mixed with molten thermoplastic from step 130. The process maycontinue with step 140 producing a highly loaded algae thermoplasticmasterbatch which may be pelletized in step 145 to form algae blendedthermoplastic pellets. The algae blended thermoplastic pellets of step145 may be further stored in step 146 for an indeterminate period beforeit is further used in a foaming or other plastic process. At step 150,any desired additives, plasticizers, compatibilizers and/or foamingagents are added to the mixture of step 140 forming athermoplastic-algae-blend designed for foaming. Thethermoplastic-algae-blend is then dispersed in step 160. In thisexample, the dispersing is performed onto a roll mill stack, but mayalso occur in a twin screw extruder along with steps 130, 140, and 150,wherein the twin screw extruder accomplishes all of these steps in acontinuous process as opposed to the batch process exemplified here. Instep 170, a final product is formed using the algae-thermoplastic blenddispersed from step 160. In an example, the final product shouldfunction and have similar, better, and/or comparable characteristics toa final product formed of a thermoplastic product formed absent thealgae content. Examples of these characteristics include mechanical,physical, rheological, degradability, or other properties of thematerial.

The present disclosure provides for an algae-based thermoplasticcomposition formed by a combination of a protein-rich algae biomass, anda resin. Protein-rich algae biomass means a biomass having at least 15%protein content by weight. In an example, a thermoplastic foam can beformed by using a foaming ingredient with the algae biomass and theresin. In one form, the algae biomass can be provided in its raw form asit is found, obtained, or produced in nature. This can include a biomassformed of microalgae, macroalgae, both microalgae and macroalgae, and/orcomponents or byproducts of these algae materials. The algae biomass canalso be provided as an extract from microalgae or macroalgae such asseaweed.

In an example, algae biomass which contains greater than 15% proteincontent by weight including greater than 20%, greater than 25% proteincontent and greater than 30% protein content can be desirable forthermoplastic compositions. Protein content has shown to havethermoplastic characteristics making it more than just a fillerincluding but not limited to a viscoelastic modulus, the ability to takeon the rheological characteristics and flow align to a melt, the abilityto change shape under temperature and pressure, and othercharacteristics. These characteristics are not exhibited by thecarbohydrates or mineral content found in algae which behave as fillersonly. In addition, to extracting to achieve a desired composition, aless energy intensive and more economical alternative to existingprocesses, includes using multiple algae sources wherein each algaesource used has naturally high levels of a targeted compound andblending them to achieve a biomass composition with desired qualities.

In an example, diatoms, coccalithophores, coralline and other algaesources high in mineral content may be used to form a desiredthermoplastic composition wherein higher mineral contents are desiredsuch as when a higher loading by weight is desired since the density ofthe mineral allows for a greater inclusion rate in a polymer beforepolymer/filler phase interactions begin to break down. Blue green algae,also known as cyanobacteria and microalgae or single cellular algaeespecially from the phylum chlorophyta, tend to be naturally high inprotein especially when collected from nutrient rich environments suchas might exist when collected from environmental remediation efforts,wastewater treatment, or as a post extracted meal from biofuelsextraction. Common types of algae found naturally include chlorella,scenedesmus, spirulina, chlamydomonas, chlorococcum, phormidium,oscillatoria, spirogyra, chroococcus, dunaliella, prasiola, nostoc, andvaucheria. High protein content is desirable in many applicationsbecause it behaves like a thermoplastic, when combined with the resin,and therefore, processes more effectively in processes that haverheological constraints and contributes its own polymericcharacteristics to the bulk properties of the material. In addition,algae high in protein has higher levels of bioavailable nitrogen andphosphorus which when used with biodegradable polymers greatly enhancesthe rate and circumstances in which biodegradation will occur making theproduct better suited for biodegradation in environments it otherwisemay not have been usable. Typically found commercially, biodegradablepolymers are unfilled or filled with starch, which lack these nutritivecharacteristics leading to slower biodegradation and no plant growthstimulation. However, this can be troubling for composting environments.The industrial composting environments for which these products aredesigned, suffer from their introduction since they only provide sourcesof carbon, which composters have in abundance, and composters need tomaintain an adequate ratio of Carbon to Nitrogen to achieve fastbiodegradation. The desired ratio is typically 25 to 30 grams of Carbonper gram of Nitrogen. Excess carbon produces slow composting and lowerquality compost that facilities are not able to sell as easily. Excessnitrogen produces to fast of a biodegradation rate and leads to stinkycompost from the growth of less desirable microorganisms that do notcompete as well as under the proper carbon to nitrogen ratio conditions.

In an example, the present disclosure provides for a product having apolymer with 20% algae by weight with a protein-rich content around 40%.Using a standard protein to nitrogen conversion factor of 6.25, meansthe product would contain about 1.25% nitrogen by weight obtaining an 80to 1 carbon to nitrogen ratio which is about 3 times the desired ratio.However, this is a significant improvement over traditionalbiodegradable resins available which typically have a carbon to nitrogenratio in excess of 300 to 1 of carbon to nitrogen. This reduces thedemands on industrial composters to find food waste and animal manureswhich are rich in nitrogen to offset the lack of nitrogen inbiodegradable polymers. For instance, studies have shown that a ratio ofabout 42 parts nitrogen rich compost from food or animal waste to 1-parttraditional polymer are necessary to achieve a proper carbon to nitrogenratio in compost. In contrast the protein-rich algae compositionsdisclosed herein would need about 4 parts of nitrogen rich material toevery 1 part of protein-rich algae biodegradable composite. Therefore,about 10 times as much biodegradable material can be composted for theavailable animal and food waste used by composting facilities withoutslowing down productivity of the facility when using the compositiondisclosed herein. Other protein-rich sources from animals or plants arenot commercially available because they are either very expensive toproduce or in most cases directly compete with food production, but thealgae described herein is widely abundant in adequate protein contentranges and does not interfere with food production and in many cases itsremoval improves food production. Therefore, algae compositions asdescribed herein are uniquely well suited to provide these benefits tobiodegradable materials.

Macroalgae, such as seaweeds, tend to be high in carbohydrates includingstructural carbohydrates and food storage carbohydrates such as starch.Carbohydrates, unless chemically modified, do not tend to behave like apolymer. Typically, they are thermally sensitive and tend to burnundergoing Maillard and caramelization reactions. Carbohydrates alsogenerate lower filler loadings by weight compared to mineralized biomasssources because they are less dense. Therefore, increased carbohydratecontent tends to be the less desirable unless significant extractionwork and or chemical modification work is conducted such ashydroxypropylation of the carbohydrates to improve their intermolecularinteractions. However, fibers can be obtained from algae rich incarbohydrates which can be used as reinforcing fillers with anisotropiccharacteristics. These can be helpful in scenarios in which achieving amaximized toughness or strength in one direction is desired, forexample, with respect to fiber, coating, or film manufacturing.

Protein-rich algae biomass can be sourced from marine, brackish, and/orfreshwater algae sources including those from the following families ofalgae: Cyanophyta, Charophyta, Chlorophyta, Phaeophyta, Chrysophyta,Bacillariophyta, Haptophyta, and Rhodophyta. Microalgae or unicellularalgae sources can be used because these species grow relatively fast,are naturally high in protein, are effective at removing water-borne andair-borne pollutants and are considered a nuisance in many bodies ofwater. In some circumstances these microalgae may even form blooms whichare larger than normal concentrations of these organisms proliferatingin a particular area, which can have destructive effects on theecosystem and local economies. Therefore, it can be helpful to removethese microalgae from ecosystems with an overabundance of nutrients toprevent or mitigate the damage from blooms. The nutrient richconditions, where these destructive blooms of microalgae are typicallyfound, can include the fastest growing and most protein-rich algalspecies. These species of algae can exhibit beneficial thermoplasticcharacteristics due to protein contents natural tendency to denatureunder elevated heat and/or pressure. This denaturation quality ofproteins allows them in typical plastic processing environments to losetheir initial form and conform to the optimal form driven by theprocessing of the thermoplastic melt. This allows these protein-richalgae compositions to outperform most other algae types in mostthermoplastic applications because they process more easily and reducethe overall internal stress in the finished part since they conform tothe desired finished parts shape in their denatured state more readily.This is especially important in flexible thermoplastic applicationswhere the structural rigidity of carbohydrate rich or ash rich algaebiomass works against the desired properties of the finished parts.

In yet another embodiment, macroalgae may be used. In one example, themacroalgae is used when an extracted meal from macroalgae is formed,which eliminates or reduces the concentration of structural and foodstorage carbohydrates naturally produced in these species.

In yet another example of the present disclosure, the composition ofalgae biomass includes a dry weight of 15 to 90% protein including 20 to85%, 25 to 80% as well as 30 to 75%, 5 to 50% carbohydrates by weightincluding 10 to 45% as well as 15 to 40%, and 5 to 80% mineral orinorganic ash content by weight including 10 to 75% as well as 15 to70%. In another example, the algae biomass includes a dry weight of35-50% protein, 5-30% carbohydrate and 25-40% ash and sourced from algaegrown from a waste water facility in a controlled environment. In aneven further example, the algae biomass includes dry weight of 41%protein, 26% carbohydrate and 33% ash and sourced from wild grown algae.

In yet a further example, the moisture content of the algae is less than15% by weight including less than 10% as well as less than 5%.Increasing moisture content increases the insulation of the materialfrom overheating and forming agglomerates while blending into thethermoplastic. However, for manufacturing, it also increases demands onventing and screw design to handle the elevated moisture content andsteam formed. Moisture contents of less than 0.5% including less than 1%as well as less than 2% and 3% are less desirable in the algae sincethey significantly increase the risks for burning the algae before it isincorporated.

In another form, the algae is milled to an average particle size with ad99 less than about 200 micron including a d99 less than about 140microns as well as a d99 less than about 80 microns and further lessthan 50 microns. Further the average particle size used should includeabout 1 to 80 micron including 5 to 70 micron as well as 10 to 60micron. Larger particle sizes should be selected in some cases sincesmaller particle size may increase the risk of agglomerate formation.However, especially in the case of thin films and fibers, smallparticles may be needed because protein-rich biomass only has someability to change its shape in a melt flow. These smaller particles willallow the biomass to pass through screen packs and/or reach a targetsize of the fiber or films.

In addition to tailoring the characteristics of an end product bychanging the composition of the algae biomass the addition and selectionof a compatibilizer can change a resulting characteristic of athermoplastic composition. A compatibilizer is not always required andis understood to confer benefits only under certain circumstances. Thisis especially true in the case of protein-rich compositions since theydo not necessarily act only as fillers and the addition ofcompatibilizers can tend to cause the algae biomass to act more as afiller in the polymer matrix and eliminates the polymericcharacteristics of the material.

Compatibilizers can be used to facilitate and enhance polymerization andcombining of algae biomass to the resin when forming a desired compositematerial. Compatibilizers have been shown to be effective whentoughening or strength enhancing characteristics of the desired materialor composition are desired. In some circumstances, elongation, DinAbrasion and other characteristics of the material can be compromisedwith the presence and use of a compatibilizer. Compatibilizers can beselected from any class of commercially available compatibilizer. Commoncompatibilizers include those having glycidyl methacrylate, butylacrylate and maleic anhydride functionalization. Compatibilizers withthis type of functionalization tend to be block copolymers or a graftedcompatibilizer, but reactive compatibilizers or coupling agents may alsobe used. These include but are not limited to coupling agents such asperoxides, isocyanates, glyoxal and other known coupling agents. Otherprocessing aids such as rheology modifiers, surfactants, plasticizers,dispersing aids, antioxidants, flame retardants, moisture scavengers andothers may be added, but are not always required. In prior examples,using these aids especially in the case of plasticizers was thought tobe effective, but in the present disclosure, plasticizers are rarelynecessary and often may lead to the formation of more agglomerates inthe algae biomass due to a slower incorporation of the biomass caused bylubrication of the polymer melt and an increase of the polymer meltsviscosity due to poor shear heating. Plasticizer use is rare incommercially applications, but in conditions when very high algaecontents are desirable, plasticizers may provide a considerable benefit.Processing aid use and selection will depend on the product propertiesdesired as well as a need to address processing hurdles, which arisewhen working with a thermoplastic composition. In yet another example,the composition is formed in the absence of a plasticizer.

The base resins suitable for use with algae to form a desiredthermoplastic composition include a broad range of resins including butnot limited to synthetic, plant-based, bio-based, renewably-sourced,petroleum-sourced resins and combinations thereof. In an example, theresins include: polyesters such as polyethylene terephthalate (PET),polybutylene terephthalate (PBT), polyethylene terephthalate glycol(PETG), polytrimethylene terephthalate (PTT), polycarbonate, and others,biodegradable resins such as polylactic acid (PLA), polybutylenesuccinate (PBS), polybutylene adipate-co-terephthalate (PBAT),Thermoplastic Starch (TPS), Polycaprolactone (PCL),polyhydroxyalkanoates (PHA) and others, polyolefins such as polyethylene(PE), polypropylene (PP), polybutene (PB), polyisobutylene (PIB), andothers, thermoplastic elastomers such as thermoplastic polyurethanes(TPU), ethylene vinyl acetate (EVA), thermoplastic polyolefin elastomers(TPO), thermoplastic vulcanizates (TPV), thermoplastic copolyesters(TPE-E), thermoplastic polyamides (TPA), Thermoplastic styrenic blockcopolymers (TPS), Thermoplastic ester-ether copolymers (TPC),Thermoplastic amide-ether copolymers (TPE-A), and others, Styrenicresins such as polyacrylonitrile butadiene styrene (ABS),polyacrylonitrile styrene acrylate (ASA), polystyrene acrylonitrile(SAN), Polystyrene butadiene (SB), polystyrene (PS) and others,polyamides such as nylon and it's derivatives and vinyl containingthermoplastics such as polyvinyl chloride (PVC), polyvinyl alcohol(PVA), polyvinylidene chloride (PVDC) and others.

While these base resins are suitable for incorporation with algaebiomass, certain characteristics of a resin will make it a more suitablecandidate for processing with algae. For instance, resins with a highermelt flow index allow the algae to incorporate in sooner as well as withlower shear heat of the algae and will produce a masterbatch with betterproperties for processing in an end product manufacturing in many casesso long as sufficient melt strength is maintained. Algae which is richin protein and low in carbohydrates has been demonstrated as beingsuitable for processing at up to 250° C. without burning when shear iscontrolled and without the addition of processing aids to reduce burningso base resins with melting points below 250° C. including below 240°C., below 220° C. as well as below 200° C. are desired, especially whenno additional processing aids to address burning are being used such asantioxidants or shear reducing additives such as lubricants,plasticizers, or rheological modifiers. Further resins with elevatedprocessing temperatures can increase the likelihood of cooking thematerial and generating odors comparable to cooked plant proteins and/orfishy malodors. Higher viscosity polymers are more likely to requireprocessing aids so the lowest viscosity polymer which has a molecularweight suitable to achieve desired end product properties and which hasenough melt strength to be processed without excessive failures in partproduction. Polymers with excessively high viscosity are likely toexhibit a melt flow rate lower than 0.01 g/10 min including 0.1 g/10 minas well as 0.5 g/10 min and 1 g/10 min when measured at 190° C. with a2.16 kg test weight. Base resin selection should further consider theintended properties of the end product and be tailored to match atargeted material's properties as desired.

Thermoplastic compositions comprising algae are useful in a number ofmarkets, however foam-related markets present unique advantages. Foamsare generally higher value commodities, which have higher pricing andcustomers which are interested in telling sustainable manufacturingstories. These markets include, among others, automotive, footwear,apparel, consumer goods, sporting goods and other customers. Foams alsogo through an off-gassing period, which is standard in foammanufacturing and allows excess gas to be expelled as the foam reachesits final shape. This allows any odor generated during processing to belargely removed all at once. In addition, foams typically use lowermelting point resins such that they will go from molten to solid slowenough for internal stresses in the foam to be relieved and a betterfoam to be produced. As such, foams as a target for algae blendedthermoplastic compositions are desirable and described in detailindividually.

In an example, an algae-based foam composition is formed by acombination of algae biomass, a foaming ingredient, and a resin. Thealgae biomass can be provided in its raw form as it is found, obtained,or produced in nature. This can include a biomass formed of microalgae,macroalgae, both microalgae and macroalgae, and/or components orbyproducts of these algae materials. In an example, the algae biomass isprotein-rich algae biomass. The algae biomass can also be provided as anextract from microalgae or macroalgae such as seaweed.

The foaming ingredient or ingredients are provided to trigger or producea foam when combined with the biomass and the resin. This can include acatalyst and/or a compatibilizer operable to facilitate combining thealgae biomass with the resin. In an example, the resin and the foamingingredient are sufficient to produce a thermoplastic.

The resin can include thermoplastic resins which are sufficient forfoaming. Examples include but are not limited to synthetic, plant-based,bio-based, renewably-sourced, petroleum sourced resins and combinationsthereof. The resins further are resins suitable for use with algae asdescribed previously.

In an example, algae biomass contains a dry weight fraction of proteinof at least 15% and up to about 90% In another example, the dry weightfraction of protein can be found in a range from about 25% to about 80%,and in yet a further example the range is from about 30% to about 70%.These ranges can be modified and include variations of protein weightfraction from about 20% to about 80%, about 20% to about 70%, or fromabout 25% to about 90%, from about 25% to about 70%, and from about 30%to about 90%, and from about 30% to about 80%.

The protein fraction of the algae biomass composition can contributemany of the desirable characteristics achieved in the resulting foam andfoam end products. Proteins react to heat and pressure by denaturing andunfolding to form moldable polymers, which can then take on a targetedshape for an end product. This plastic-like characteristic in the heatedor molten state of a composite allows for better foam properties withless of the negative characteristics associated with using fillers infoams. Additionally, the proteins contain function in both hydrophilicand hydrophobic regions allowing some compatibility with most polymersystems which tend to be largely hydrophobic. However, in someembodiments, proteins in the presence of small molecule carbohydratessuch as mono- and di-saccharides can crosslink to each other in Maillardreactions and form small accumulations of proteinaceous material calledagglomerates which can harm the foam properties.

In an example, the dry weight carbohydrate fraction of the algae biomasscomposition is about 50% or less. In another example, the dry weight ofthe algae biomass composition is fraction is 40% or less. In someexamples, the dry weight of the algae biomass composition is fraction is30% or less. The carbohydrate fractions generally include structural andfood storage types. The structural carbohydrates can be selected fromthe group consisting of: cellulose, hemicellulose, pectin, lignin,chitin, carrageenan, suberin, cutin, agar, peptidoglycans, and othersand combinations or variations thereof. These structural carbohydratesunder heat and pressure typically do not change shape and as such, serveas structural reinforcing agents with little or no plastic likecharacteristics. This can contribute to desired features andcharacteristics of the final foam product or foam end products.

The moieties found in carbohydrates can often inhibit, interfere, and/orinteract with crosslinkers, foaming gas diffusion, cell expansion andsize, and other important aspects of foam formation. Food storagecarbohydrates can also be found in algae, including but not limited toalginate, starches like amylose amylopectin, and others. In addition tothe problems found in structural carbohydrates, food storagecarbohydrates are more temperature sensitive and readily degrade, in thepresence of moisture, to saccharides which can produce caramelization,Maillard, and other side reactions, burn readily, and yield otherconsequences which are destructive to foam properties.

A modified carbohydrate fraction may be of interest in foaming such astrans-esterification or other modification of the carbohydrates whichwould change their moieties and chemical behavior. Such modificationsmay eliminate many of the negative side effects of carbohydrates, butthese modifications may also substantially increase the cost of thebiomass and make it less economical than simply selecting compositionswhich have desired characteristics already.

If rigid foam compositions with significant structural reinforcementsare desired, increasing mineral contributions from algae in biomass canbe effective. In some examples, increasing mineral content is preferredas compared to increasing the carbohydrate weight fraction. Algae types,including but not limited to diatoms, coralline algae, coccolithophore,as well as others have been shown to mineralize a significant portion oftheir biomass and can be used to increase the targeted properties of amaterial as a functional filler. Traditional mineral fillers are alsoavailable on the market from mining and other sources, but these sourceshave a less favorable environmental impact. The use of algae biomasswith significant mineralization may be beneficial. Additionally, usingalgae derived minerals may provide added technical benefits due to thelarger surface area, which can impact nucleation and other foamingprocesses to yield more uniform cell size distributions, greater celldensity, and other improvements to foam properties. Minerals are alsoknown to be inert in the heat, pressure, and reactions during foaming,thus making them desirable candidates as structural reinforcing aids.

In a further embodiment, the algae biomass composition includes mineralshaving a dry weight ash fraction in concentrations from about 5-85%. Inanother example, the concentration of minerals in the algae biomasscomposition is between about 10-75%, and in yet another example, thefraction is between about 15-65%. The mineral fraction is a relativelydominate portion of the biomass fraction which is not protein. Theseranges can be modified and include variations of mineral dry weight ashfraction from about 10% to about 70%, about 10% to about 60%, or fromabout 15% to about 80%, from about 15% to about 60%, and from about 20%to about 80%, and from about 20% to about 70%. The dry weight ashfraction will generally include the beneficial mineralized biomass aswell as some salts and other inorganic fractions. The salt and otherinorganic fractions can be reduced if desired by washing biomass beforedrying if necessary.

In yet another embodiment, an algae-based foam product further includesa foaming ingredient that is provided to produce the foam. The foamingingredient may include but is not limited to crosslinkers,compatibilizers, plasticizers, accelerants, catalysts, blowing agents,other ingredients, and combinations thereof. Crosslinkers may includebut are not limited to peroxide based, isocyanate based, sulfur based,aziridine based, dialdehyde based, and other crosslinking agents basedon the specific polymer systems requirements. For example, dicumylperoxide may be used with Ethylene-vinyl acetate (EVA) or Polyethylene(PE); isocyanate may be used to link polymers with hydroxyl or aminemoieties as well as proteins into the foam matrix; sulfur-basedcrosslinking may be used in SBS polymer systems; glyoxal may be used tocrosslink algae and EVA, among other examples. These crosslinkersgenerally act to change the kinetics of gas flow exiting the polymermatrix to balance cell formation against gas escape and may also be usedto help compatibilize algae to the polymer matrix.

Compatibilizers are operable to aid the algae in interacting with thepolymer matrix and reduce phase separation. Since phase separation is aprincipal cause of agglomerate formation, compatibilizers can beeffective in developing foam compositions which exhibit the benefits ofalgae-based compositions without suffering undesired consequences.Compatibilizers, include but are not limited to, side chain modified andgrafted polymers, block co-polymers, crosslinkers targeting the algae,wetting agents, other compatibility aids, and combinations thereof.

Plasticizers allow for the reduction of shear which can create thermalspikes during mixing and lead to agglomerate formation, gel formation,and many other negative conditions in a foam. The necessity ofplasticizers is dependent on the mixing process used to make a foam.

Accelerants and catalysts promote a faster reaction of foaming gasrelease or crosslinking depending on where they are targeted.Accelerants and catalysts take many forms based on the targetedcrosslinker or blowing agent. Any agent which works to speed up theaction of a crosslinker or blowing agent or which allows the action of acrosslinker or blowing agent to occur in conditions it otherwise wouldnot act would be considered an accelerant or catalyst, respectively.Accelerants and catalysts can be used in circumstances in which there isan economic benefit to faster part manufacturing or the use of lessenergy. Accelerants and catalysts may also be used to reduce therequired temperature of reaction to prevent the cooking of algae and thegeneration of foul odors or to balance the rate of gas generation andcrosslinking reactions to improve foam cell formation and bubble growth.

Blowing agents are the constituents of a foam which produce a gas andgenerate cell formation, proliferation, and/or growth. Blowing agentsmay be chemical or physical blowing agents. Chemical blowing agentsproduce a gas through a decomposition reaction breaking a molecule downinto its constituent gases. Physical blowing agents are molecules whichat a certain temperature and pressure will become a gas, but exist as aliquid or solid at the operating conditions experienced prior tofoaming. Blowing-gas type selection and quantity are determined on thebasis of desired manufacturing environment, expansion ratio, moldcharacteristics, the thermoplastic polymer being used and correspondinggas saturation properties for that polymer, and/or gas yield.

Thermoplastic resins come in various chemical classes such aspolyesters, polyolefins, thermoplastic elastomers, styrenics,polyamides, polyethers, polyvinyl chlorides, polyurethanes, andcopolymer combination thereof. The thermoplastic resins can include, butnot limited to, a polymer selected from the group consisting of ethylenevinyl acetate (EVA), polyvinyl chloride (PVC), polyethylene (PE),polypropylene (PP), polystyrene (PS), polyolefin elastomers (TPO),thermoplastic polyurethane (TPU), styrene butadiene styrene and styreneethylene butylene styrene (TPR), polylactic acid (PLA), polybutyleneadipate-co-terephthalate (PBAT), polybutylene succinate (PBS),polyethylene terephthalate (PET), nylon in its various forms (PA),polybutylene terephthalate (PBT), others, and combinations thereof.These thermoplastics can determine expected bulk mechanical propertiesof a finished foam and foam end product and establish many other aspectsof a final foam composition. In an example, criteria used inthermoplastic selection includes avoiding high melting points, which canlead to cooking of the algae and foul odor generation. In an example,sufficient melting point temperatures less than 250° C. are desiredincluding temperatures less than 230° C., as well as less than 210° C.as well as temperatures less than 190° C. In a further example, theresin of the thermoplastic should have a melt flow rate in excess of0.01 g/10 min.

The present disclosure provides for a foam composition including algae,a thermoplastic, and a foaming ingredient sufficient to make analgae-based foam. The ingredients may be processed in a number of waysto generate the algae-based foam. In an example, algae is processed inorder to be suitable for inclusion into the thermoplastic with a lowrisk of agglomeration. In one form, if extraction is required to achievean algae composition which is suitable, then the extraction should bedone first. A sufficient moisture content for the algae can be less thanabout 15% moisture by weight including less than about 10% moisture byweight as well as less than about 5% moisture by weight. Moisturecontents of less than 1% including less than 2% as well as less than 3%are not desired in the algae since they significantly increase the risksfor burning the algae before it is incorporated. In another form, thealgae is milled to a particle size with a d99 less than about 200 micronincluding a d99 less than about 140 microns as well as a d99 less thanabout 80 microns. Further the average particle size used should includeabout 1 to 80 micron including 20 to 70 micron as well as 30 to 60micron.

Extracted protein meal from algae is in some cases a byproduct of otherproduct manufacturing processes. For instance, alginate, agar,nutraceuticals, biofuels and other products are extracted from algaeleaving behind protein-rich meal. This protein-rich meal may be usedas-is or in some cases may be washed or further extracted to producemeal with higher protein content, which is free of saccharides, or toremove other value-added co-products. In some cases, extraction mayimprove the properties of the resulting algae-based foam products andmay lower cost through the fractionation and valorization of usefulco-products.

Drying algae can be conducted through both mechanical and thermal means.In an example, raw microalgae biomass or extracted algae meal can beobtained as either a slurry at 0.5 to 15% by weight solids or it may beavailable as a wet cake or paste at 15-30% solids. This can then bedried to above 85% solids including greater than 90% solids as well asgreater than 95% solids in order to effectively incorporate the algaeinto a thermoplastic. In some examples, drying before the algae ismilled is effective to improve the economics, efficiency, and throughputof milling. However, in some cases milling is done on wet materials anddrying needs to be conducted on wet materials such as in wet media millslike ball mills. Mechanical drying or dewatering can be done to reducethe risks of burning and generating foul odors in addition to improvingthe economics of drying. Examples include but are not limited totechniques such as belt filter pressing, centrifuge dewatering, screwpressing, plate and frame pressing, and others. Assisted thermal dryingmay also be done and is often effective in situations including, but notlimited to, microwave drying, drum drying, heated screw drying, hot airconvective drying, spray drying, and others. Passive thermal drying suchas solar drying can also be used in some cases but increases the risk offoul odor generation due to biomass degradation if solar drying leads toprolonged periods of algae biomass storage before it is sufficientlydried. Additional directed electromagnetic wave or sound wave technologycan be used to rupture a cell before or during drying to improve waterremoval. A sufficient moisture content for the algae can be less thanabout 15% moisture by weight including less than about 10% moisture byweight as well as less than about 5% moisture by weight. Moisturecontents of less than 0.1% including less than 1% as well as less than3% are not desired in the algae since they significantly increase therisks for burning the algae before it is incorporated.

Milling algae is typically done in dry mills but in some cases wetmilling may be desired. Dry milling processes include jet mills, hammermills, media mills, air classifying mills, grinding mills, and others.Algae's friability tends to be related to its moisture content whenmilled so effective drying often means more effective milling. Algae canbe classified during milling or can be sieved after milling to obtainthe particle size targeted for the desired algae-based plasticcompositions. In the case of foams, in an example, a particle size witha d99 less than 200 microns including less than 140 microns as well asless than 80 microns can be targeted. The particle size can be reducedto the point that the algae can be readily dispersed in the polymermatrix and will not increase cell size or change cell shape whenfoaming, but unless counteracted through other actions, too fine aparticle size can lead to an increased risk of agglomerate formation.

Once the algae have been milled and dried, they are ready to beincorporated into the thermoplastic composition along with the foamingingredients sufficient to make an algae-based foam. Mixing the algaewith the thermoplastic and foaming ingredients can be done withconventional mixing equipment used in the plastics industry. Forexample, it can be blended with a Banbury mixer and two mill roll stacksor via an extruder such as a twin-screw extruder. Other mixingtechniques may be used but are not elaborated in this disclosure. Shearreduction can be a driving concern to prevent agglomerate formation. Ineither case the algae is best added to molten or semi-moltenthermoplastic to reduce the shear it experiences while mixing. In thecase of Banbury mixers, this means the thermoplastic should be addedbefore the algae and sufficiently mixed and/or plasticized to allow itto readily accept and disperse the algae before it is added.

In an example, after all of the remaining foaming ingredients sufficientto form a foam have been added in the Banbury mixer, the finishedcomposition can be further mixed and distributed on a two mill rollstack by using folding and layering techniques to achieve an evendistribution. When using the two mill roll stack the composition shouldbe kept at an elevated temp which does not begin crosslinking or beginto set off foaming, but reduces the viscosity of the composition as muchas possible. This will help to reduce high shear and prevent agglomerateformation. Additionally, the gap between rollers can be adjusted to awider gap distance and more passes through the two mill roll stack canbe used to further reduce the risk of high shear and agglomeration.After the two mill roll stack step, the composition should have thealgae sufficiently dispersed therein and distributed in order to foamand can be further worked and foamed to achieve a desired foam product.

In a further example, the algae is mixed via extruder, like a twin-screwcorotating extruder. The twin-screw extruder offers flexibility inmixing conditions allowing the user to control shear and preventagglomerate formation and it is a continuous process making the algaecomposition production more efficient and reducing cost. When mixed in atwin-screw extruder, the thermoplastic and other non-shear sensitiveingredients should be added in the feed throat and should be mixed in aback section of the extruder with high shear mixers and high heat toproduce a consistent and low viscosity melt flow quickly. The algae,along with other shear sensitive ingredients, should then be addeddownstream via side feeders or comparable feeding equipment at whichpoint barrel temperature can be lowered and low shear distributivemixing elements can be used. Similar techniques can be applied withsingle screw or counterrotating twin screw extruders, however they aremore limited in terms of shear reduction and flexibility of screwdesign. Since extruders generally produce pellets the final compositioncan readily be used in most types of foaming equipment without problems.

The protein-rich algae compositions described herein, when foameddemonstrate novel properties which are beneficial in some situations.Benefits of the algae-based foam compositions detailed herein includeenhanced surface polarity, tailorable material property benefits, carbonsequestration and carbon credit generation, and other environmentalbenefits. The protein-rich algae compositions described herein whenfoamed demonstrate novel properties which are beneficial. Enhancedsurface polarity provides a benefit in water borne adhesive bonding andbond strength which provides benefits to many markets. Additionally, ithas implications to oil resistance and repellency, oil slip resistance,and paint and coating options allowing more environmentally friendlyoptions to be used.

Algae based foam compositions also exhibit tailorable properties withratios of protein to mineral content being controllable which can varyfoam properties to achieve the targeted performance characteristics.Compared to other renewable feedstock options these characteristicsachieved through the diversity of algae available is unique and allowsfor more flexibility in foam product specifications. Additionally, giventhe positive environmental impacts of algae removal as well as the fastgrowth, and low impact of acquisition algae offers many environmentalbenefits over other renewable material options that exist in the marketcurrently including but not limited to a route to carbon sequestrationand its accepted use as a carbon credit generating commodity.

An example algae-based foam product includes 40% algae by weight and thebalance is resin. Depending on the intended end use, the algae fractioncan be modified. For example, if forming a flexible foam for use infootwear and shoe components, up to 30% algae can be incorporated with adesired thermoplastic resin. An algae-based thermoplastic foam may havea density that ranges from about 1 or 5 or 10 to 30 to about 100 or 200or 300 to about 400 kg/m³ or more.

An example algae-based solid good includes up to 45% algae by weight andthe balance is resin. Depending on the intended end use, algae fractioncan be modified. For example, if forming a flexible solid good such asan outsole for use as a shoe components, up to 30% algae may be addedwhich is protein-rich, whereas for a rigid part such as a shoe shank forus as a shoe component or marine shellfish traps up to 30% algae may beadded which is high in mineral rich algae for structural reinforcement.The solid good may have a density from 400 or 600 or 800 to 1500 or 2000or 2500 kg/m3 or more.

An example algae-based film or fiber good includes up to 25% algae byweight and the balance is resin. Depending on the end use, the algaefraction may be modified. For example, if forming a flexible film orfiber up to 15% algae may be added which is protein-rich, where as arigid fiber may incorporate more of mineral rich algae for structuralreinforcement. The film or fiber may have a thickness from 1 micron or10 micron or 25 micron to 1 cm or 2 cm or 3 cm or more.

Masterbatch can be defined as a solid additive for plastic used forimparting properties to plastics (additive masterbatch). Masterbatch istypically a concentrated mixture of additives encapsulated during a heatprocess into a carrier resin which is then cooled and cut into agranular shape. Masterbatch allows the processor to form polymereconomically during the plastics manufacturing process. Masterbatch alsoallows for greater economies of scale in production since onemasterbatch maybe used in multiple product compounds to achieve a widerange of product properties. In an example, a thermoplastic masterbatchmay be made from an environmental mixed culture of microalgae having 39%protein and 28% ash wherein the thermoplastic masterbatch is suitablefor the production of thermoplastic foam products. In another example, athermoplastic masterbatch may be made from a freshwater macroalgaesource such as Ulva with 20% protein and 31% ash blended with acyanobacterial algae source, which is naturally very high in protein ataround 68% protein and 8% ash at an equal ratio such that the finalmixed algae composition is around about 44% protein and 20% ash. Sincethe final algae composition has a similar range of protein to ash ratiosand both sources contain very little carbohydrate, the masterbatcheswere found to be capable of being used interchangeably and were bothcapable of producing the same outcome in a foam product.

In a further example, a thermoplastic foam product produced with algaeand a thermoplastic elastomer such as EVA generates a foam withproperties suitable for footwear products with densities ranging from0.05 g/cm3 to 0.9 g/cm3, a hardness from 10 to 80 Asker C, a compressionset from 30% to 80%, a rebound from 20% to 70%, a Din Abrasion from 400to 100 mm, a tear strength from 1 to 20 kg/cm, and an algae content from1 to 35% algae.

In yet another example, a thermoplastic injection molded productproduced with algae and a thermoplastic elastomer such as SBS or SEBSgenerates an injection molded good with properties suitable for footwearproducts with densities from 0.1 g/cm3 to 1.3 g/cm3, a hardness from 75to 35 shore A, a Din Abrasion from 300 to 80 mm, tear strength from 5 to50 kg/cm, and an algae content from 1 to 40% algae.

In still yet another example, thermoplastic foam product produced withalgae and a thermoplastic elastomer with olefin chemistry (TPO)generates a foam with properties suitable for footwear products having adensity from 0.05 g/cm3 to 0.9 g/cm3, a hardness from 10 to 80 Asker C,a compression set from 30% to 80%, a rebound from 20% to 70%, a DinAbrasion from 400 to 100 mm, a tear strength from 1 to 20 kg/cm, and analgae content from 1 to 35% algae.

In yet another form, a thermoplastic film product produced with algaeand a thermoplastic elastomer and biodegradable polymer polybutyleneadipate-co-terephthalate (PBAT) generates a thermoplastic film withproperties suitable for agricultural purposes with a thickness from 0.1to 10 mil, a tear strength from 100 to 10,000 gf, a tensile strength atbreak from 500 to 100,000 psi and an algae content from 1 to 20% algae.

In still yet another form, a thermoplastic product is produced withalgae where a biodegradable base resin is used. Wherein the degradationof the algae polymer composite was found to enhance plant growth witharound about a 300% improvement in above ground plant foliageproduction. In a further example, the biodegradable base resin wascapable of passing an ASTM D6400 industrial testing protocol in 9months, but when used in the algae based composite the new algae basedmaterial biodegraded in industrial composting conditions in 4 to 5months and was found to even take on marine biodegradabilitycharacteristics degrading in marine field tests in under a year. Thepart was also found to enhance the parts home composting degradationrate. The enhanced biodegradability and plant growth stimulation isexpected to be imparted by the incorporation of algae biomass into themasterbatch and is specifically enhanced by the nutritive contributionsof the protein-rich algae meal. Protein-rich algae meal can be found toprovide an excellent source of nitrogen and is often found to containpotassium and/or phosphorus sources in excess of 1% of the biomass byweight. The nitrogen, phosphorus, and potassium sources are generallyfound as organic compounds stored in the biomass which are encased inbiodegradable polymer. The release of nutrients is therefore dependenton the polymeric materials biodegradation rate and is found to be slowrelease preventing over fertilization and fertilizer burns to plantroots which negatively impact plant health.

The addition of algae alongside non-degradable polymers with additivessuch as enzymes, bacterial signal molecules, positive chemotaxis agentsor other chem attractants and/or swelling agents, water attractants,additives that increase free volume or enhance water absorption rate andhydrophilicity of a polymer substrate may further enhance abiodegradability that can be produced especially in anaerobic conditionssuch as a landfill. Wherein algae can be used as an enhancing agent tocommercially available landfill biodegradation additives fornon-biodegradable polymers.

The present disclosure has been described both in general and in detailby way of examples. Persons skilled in the art will understand that thedisclosure is not limited necessarily to the specific aspects disclosed.Modifications and variations can be made without departing from thescope of the disclosure as defined by the following claims or theirequivalents, including equivalent components presently known, or to bedeveloped, which can be used within the scope of the present disclosure.Hence, unless changes otherwise depart from the scope of the disclosure,the changes should be construed as being included herein.

We claim:
 1. An algae-based thermoplastic composition comprising: (a) aprotein-rich algae biomass selected from either microalgae, macroalgaeor combinations thereof, wherein the protein content is greater than orequal to 15% by weight of the algae biomass and the algae biomass isdried to a moisture content of less than or equal to 15% by weight andhaving a particle d99 of up to 200 microns, wherein the dried algaebiomass is at least 5% by weight of the thermoplastic composition; and(b) a resin selected from the group consisting of: biodegradablepolymers, polyesters, polyolefins, thermoplastic elastomers, styrenics,polyamides, polyethers, polyvinyl chlorides (PVC), thermoplasticpolyurethanes (TPU), polybutylene adipate-co-terephthalate (PBAT),polyethylene (PE), ethylene-vinyl acetate (EVA), and combinationsthereof.
 2. The thermoplastic composition of claim 1, wherein the resinis configured to exhibit rheological properties suitable for blendingwith algae including a melting temperature less than 250° C. and a meltflow rate in excess of 0.01 g/10 min.
 3. The thermoplastic compositionof claim 1, wherein the algae biomass is provided having a proteincontent of greater than 20% by weight.
 4. The thermoplastic compositionof claim 1, wherein the algae biomass comprises a member from the groupconsisting of cyanobacteria and a Cyanophyta, Charophyta, Chlorophyta,Phaeophyta, Chrysophyta, Bacillariophyta, Haptophyta, and Rhodophytaphylum microalgae.
 5. The thermoplastic composition of claim 1, whereinthe algae biomass is sourced from a plurality of algae sources includinga member from the group of mineral rich algae consisting of diatoms,coccalithophores, coralline and combinations thereof.
 6. Thethermoplastic composition of claim 1, wherein the algae biomasscomprises a dry weight of 15 to 90% protein, 5 to 50% carbohydrates, and5 to 80% mineral and/or inorganic ash content.
 7. The thermoplasticcomposition of claim 1, wherein the algae biomass comprises a dry weightof 20 to 85% protein, 10% to 45% carbohydrate, and 10 to 75% mineraland/or inorganic ash content.
 8. The thermoplastic composition of claim1, wherein the algae biomass comprises a dry weight of 25 to 80%protein, 15% to 40% carbohydrate, and 15 to 70% mineral and/or inorganicash content.
 9. The thermoplastic composition of claim 1, wherein thealgae biomass comprises a dry weight of 35-50% protein, 5-30%carbohydrate and 25-40% mineral and/or inorganic ash content.
 10. Thethermoplastic composition of claim 1, wherein the algae biomass isprovided as a powder milled to an average particle size between 1 and 80micron.
 11. The thermoplastic composition of claim 1, further comprisinga compatibilizer provided to increase compatibility of the algae biomasswith the resin, the compatibilizer having functionalization selectedfrom the group consisting of side chain modified polymers, blockcopolymers, grafted compatibilizer, reactive compatibilizers withglycidyl methacrylate, butyl acrylate, maleic anhydride groups orcoupling agents selected from the group consisting of peroxides,isocyanates, and glyoxal.
 12. The thermoplastic composition of claim 1,wherein the resin further comprises a member selected from the groupconsisting of synthetic, plant-based, bio-based, renewably-sourced,petroleum sourced resins and combinations thereof.
 13. The thermoplasticcomposition of claim 1, wherein the resin is selected from the groupconsisting of polyesters, polyethylene terephthalate (PET), polybutyleneterephthalate (PBT), polyethylene terephthalate glycol (PETG),polytrimethylene terephthalate (PTT), polycarbonate, biodegradableresins, polylactic acid (PLA), polybutylene succinate (PBS),polybutylene adipate-co-terephthalate (PBAT), polyhydroxyalkanoates(PHA), polyolefins such as polyethylene (PE), polypropylene (PP),polybutene (PB), polyisobutylene (PIB), thermoplastic elastomers such asthermoplastic polyurethanes (TPU), ethylene vinyl acetate (EVA),thermoplastic polyolefin elastomers (TPO), thermoplastic vulcanizates(TPV), thermoplastic copolyesters (TPE-E), thermoplastic polyamides(TPA), thermoplastic styrenic block copolymers (TPS), thermoplasticester-ether copolymers (TPC), thermoplastic amide-ether copolymers(TPE-A), polyacrylonitrile butadiene styrene (ABS), polyacrylonitrilestyrene acrylate (ASA), polystyrene acrylonitrile (SAN), polystyrenebutadiene (SB), polystyrene (PS) nylon, polyvinyl alcohol (PVA),polyvinylidene chloride (PVDC) and combinations thereof.
 14. Athermoplastic composition of claim 1 wherein the thermoplasticcomposition is configured for use in processes selected from injectionmolding, blow molding, roto molding, cast film extrusion, blown filmextrusion, bun foaming, injection foaming, compression foaming, profileextrusion, steam chest expansion foaming, autoclave foaming andcombinations thereof.
 15. The thermoplastic composition of claim 1,further comprising a foaming ingredient selected from the group ofadditives consisting of crosslinkers, peroxide-based crosslinkingagents, isocyanate-based crosslinking agents, sulfur-based crosslinkingagents, aziridine-based crosslinking agents, dialdehyde-basedcrosslinking agents, compatibilizers, plasticizers, accelerants,catalysts, blowing agents, and combinations thereof, wherein the foamingingredient is configured to forming a thermoplastic biodegradable foamproduct.
 16. The thermoplastic composition of claim 15, wherein thebiodegradable resin is selected from the group resins consisting ofpolybutylene adipate-co-terephthalate (PBAT), polybutylene succinate(PBS), polylactic acid (PLA), polyhydroxyalkanoates (PHA), thermoplasticstarch (TPS), and polycaprolactone (PCL).
 17. A solid product comprisingthe thermoplastic composition of claim 1, wherein the composition isprovided having a density from 400 to 2500 kg/m3.
 18. A film comprisingthe thermoplastic composition of claim 1, wherein the compositiondefines a thickness from 1 micron to 3 cm.
 19. A fiber comprising thethermoplastic composition of claim 1, wherein the composition defines athickness from 1 micron to 3 cm.
 20. The thermoplastic composition ofclaim 1, wherein the algae biomass composition is added alongside achemoattractant or swelling agents configured to make non-degradableresins biodegradable such that a biodegradable substrate with anaerobicbiodegradation is produced.